Oxidative–elimination reactions of zerovalent iron and ruthenium complexes

Abstract
Ultraviolet irradiation of a solution of trans-(Et3P)2Fe(CO)3 in liquid sulphur dioxide gives trans-(Et3P)2Fe(CO)2(SO2), which reacts with hydrogen iodide to form cis-(CO)2-trans-(Et3P)2Fel2. Treatment of trans-(PhPMe2)2Fe(CO)3 with iodine or hydrogen iodide affords cis-(CO)2-trans-(PhPMe2)2Fel2. trans-(Ph2PMe)2Ru(CO)3 and iodine react to give cis-(CO)2-trans-(Ph2PMe)2Rul2, whereas, a mixture of isomers of (CO)2[EtC(CH2O)3P]2Rul2 is obtained from trans-[EtC(CH2O)3P]2Ru(CO)3 and iodine. Trifluoroacetic acid reacts with trans-[(MeO)3P]2Ru(CO)3 to form cis-(CO)2-trans-[(MeO)3P]2Ru(O2CCF3)2. Treatment of trifluoroiodomethane with trans-[EtC(CH2O)3P]2Ru(CO)3 gives cis-(CO)2-trans-[EtC(CH2O)3P]2Ru(CF3)l, whereas, trans-(PhPMe2)2Fe(CO)3 gives an isomeric mixtures (CO)2(PhPMe2)2Fe(CF3)l. trans-L2Ru(CO)3(L = Ph2PMe, or PhPMe2) react with methylene chloride to give the respective dichlorides.
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